Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species
Abstract
Studies of the complexation of new promising ligands with uranyl (UO22+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO22+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO22+, VO2+, and VO2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques, along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO22+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO22+, VO2+, and VO2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, andmore »
- Authors:
-
- Univ. of North Carolina Wilmington, NC (United States). Dept. of Chemistry and Biochemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1329747
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 20; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
Citation Formats
Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, and Hancock, Robert D. Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species. United States: N. p., 2016.
Web. doi:10.1021/acs.inorgchem.6b02234.
Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, & Hancock, Robert D. Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species. United States. https://doi.org/10.1021/acs.inorgchem.6b02234
Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, and Hancock, Robert D. Fri .
"Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species". United States. https://doi.org/10.1021/acs.inorgchem.6b02234. https://www.osti.gov/servlets/purl/1329747.
@article{osti_1329747,
title = {Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species},
author = {Lashley, Mark A. and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Dai, Sheng and Hancock, Robert D.},
abstractNote = {Studies of the complexation of new promising ligands with uranyl (UO22+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO22+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO22+, VO2+, and VO2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques, along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO22+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO22+, VO2+, and VO2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO22+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.},
doi = {10.1021/acs.inorgchem.6b02234},
journal = {Inorganic Chemistry},
number = 20,
volume = 55,
place = {United States},
year = {Fri Sep 30 00:00:00 EDT 2016},
month = {Fri Sep 30 00:00:00 EDT 2016}
}
Web of Science
Figures / Tables:
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